Shaheen Sultana, Rajorshi Mandal and Kumar Biradha*,
{"title":"探索刚性和线性二烯配位聚合物中的固态 [2 + 2] 光二聚化:二维配位聚合物到三维配位聚合物的单晶到单晶转化","authors":"Shaheen Sultana, Rajorshi Mandal and Kumar Biradha*, ","doi":"10.1021/acs.cgd.4c00614","DOIUrl":null,"url":null,"abstract":"<p >Coordination polymers serve as an important platform to promote highly selective solid-state reactions between organic struts. A new class of amide-containing cyclobutane molecules has been synthesized using a [2 + 2] photodimerization reaction in coordination polymers (CPs) of rigid and linear diene 3,3′-(1,4-phenylene)bis(<i>N</i>-(3-pyridyl)acrylamide), <b>4PMA</b>, with rigid as well as flexible dicarboxylates as coligands. Four Co(II) CPs studied here produce 2D layers with rhomboidal grids (isophthalate (<b>CP-1</b>) and <i>p</i>-carboxy cinnamate (<b>CP-2</b>)), while <i>p</i>-phenylene acrylate (<b>CP-3</b>) yields a 3D framework with <b>cds</b> topology and <i>p</i>-phenylene diacetate forms 2D layers with a bimetallic secondary building unit (SBU). The [2 + 2] cycloaddition reaction upon exposure to 365 nm UV light on the methanol solvate of <b>4PMA</b> remained elusive despite a favorable polymeric alignment in its crystal structure. Single crystals of CPs upon irradiation resulted in photodimerization; however, the crystal structure suggests polymerization (<b>CP-1</b> and <b>CP-2</b>) or no reaction (<b>CP-3</b>). This unusual behavior is attributed to deviations in geometrical parameters from the ideal, serving as the driving force behind the photodimerization reaction. Nevertheless, the 2D CP of <b>CP-4</b> exhibited resilience during dimerization, leading to the formation of a 3D coordination polymer of the <b>fsc</b> net of <b>CP-4P</b> through a single-crystal-to-single-crystal structural transformation. The separated dimer product displays quenched photoluminescence and blue-shifted spectra compared with the monomer.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Exploration of Solid-State [2 + 2] Photodimerization in the Coordination Polymers of Rigid and Linear Diene: Single-Crystal-to-Single-Crystal Transformation of a 2D Coordination Polymer to a 3D Coordination Polymer\",\"authors\":\"Shaheen Sultana, Rajorshi Mandal and Kumar Biradha*, \",\"doi\":\"10.1021/acs.cgd.4c00614\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Coordination polymers serve as an important platform to promote highly selective solid-state reactions between organic struts. A new class of amide-containing cyclobutane molecules has been synthesized using a [2 + 2] photodimerization reaction in coordination polymers (CPs) of rigid and linear diene 3,3′-(1,4-phenylene)bis(<i>N</i>-(3-pyridyl)acrylamide), <b>4PMA</b>, with rigid as well as flexible dicarboxylates as coligands. Four Co(II) CPs studied here produce 2D layers with rhomboidal grids (isophthalate (<b>CP-1</b>) and <i>p</i>-carboxy cinnamate (<b>CP-2</b>)), while <i>p</i>-phenylene acrylate (<b>CP-3</b>) yields a 3D framework with <b>cds</b> topology and <i>p</i>-phenylene diacetate forms 2D layers with a bimetallic secondary building unit (SBU). The [2 + 2] cycloaddition reaction upon exposure to 365 nm UV light on the methanol solvate of <b>4PMA</b> remained elusive despite a favorable polymeric alignment in its crystal structure. Single crystals of CPs upon irradiation resulted in photodimerization; however, the crystal structure suggests polymerization (<b>CP-1</b> and <b>CP-2</b>) or no reaction (<b>CP-3</b>). This unusual behavior is attributed to deviations in geometrical parameters from the ideal, serving as the driving force behind the photodimerization reaction. Nevertheless, the 2D CP of <b>CP-4</b> exhibited resilience during dimerization, leading to the formation of a 3D coordination polymer of the <b>fsc</b> net of <b>CP-4P</b> through a single-crystal-to-single-crystal structural transformation. 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Exploration of Solid-State [2 + 2] Photodimerization in the Coordination Polymers of Rigid and Linear Diene: Single-Crystal-to-Single-Crystal Transformation of a 2D Coordination Polymer to a 3D Coordination Polymer
Coordination polymers serve as an important platform to promote highly selective solid-state reactions between organic struts. A new class of amide-containing cyclobutane molecules has been synthesized using a [2 + 2] photodimerization reaction in coordination polymers (CPs) of rigid and linear diene 3,3′-(1,4-phenylene)bis(N-(3-pyridyl)acrylamide), 4PMA, with rigid as well as flexible dicarboxylates as coligands. Four Co(II) CPs studied here produce 2D layers with rhomboidal grids (isophthalate (CP-1) and p-carboxy cinnamate (CP-2)), while p-phenylene acrylate (CP-3) yields a 3D framework with cds topology and p-phenylene diacetate forms 2D layers with a bimetallic secondary building unit (SBU). The [2 + 2] cycloaddition reaction upon exposure to 365 nm UV light on the methanol solvate of 4PMA remained elusive despite a favorable polymeric alignment in its crystal structure. Single crystals of CPs upon irradiation resulted in photodimerization; however, the crystal structure suggests polymerization (CP-1 and CP-2) or no reaction (CP-3). This unusual behavior is attributed to deviations in geometrical parameters from the ideal, serving as the driving force behind the photodimerization reaction. Nevertheless, the 2D CP of CP-4 exhibited resilience during dimerization, leading to the formation of a 3D coordination polymer of the fsc net of CP-4P through a single-crystal-to-single-crystal structural transformation. The separated dimer product displays quenched photoluminescence and blue-shifted spectra compared with the monomer.
期刊介绍:
The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.